CN110128250A - The method for preparing cyclohexanone - Google Patents

The method for preparing cyclohexanone Download PDF

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Publication number
CN110128250A
CN110128250A CN201810136077.XA CN201810136077A CN110128250A CN 110128250 A CN110128250 A CN 110128250A CN 201810136077 A CN201810136077 A CN 201810136077A CN 110128250 A CN110128250 A CN 110128250A
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titanium
molecular sieve
catalyst bed
agent
catalyst
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CN110128250B (en
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史春风
林民
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to Cyclohexanone Production field, the method for preparing cyclohexanone is disclosed, comprising: under oxidation reaction condition, the liquid mixture containing hexamethylene alcohol and oxidizing agent is made to flow through catalyst bed；The catalyst bed includes the first catalyst bed and the second catalyst bed, and on the basis of the flow direction of liquid mixture, first catalyst bed is located at the upstream of second catalyst bed；First catalyst bed is filled with Titanium Sieve Molecular Sieve；Second catalyst bed is filled with titanium Si-Al molecular sieve.Method of the invention can obtain higher oxidant conversion ratio and cyclohexanone selectivity.

Description

The method for preparing cyclohexanone
Technical field
The invention belongs to Cyclohexanone Production fields, and in particular, to a kind of titanium Si-Al molecular sieve is in cyclohexanol Using especially a kind of method for preparing cyclohexanone.
Background technique
Cyclohexanone is a kind of important industrial chemicals, is widely used in fiber, synthetic rubber, industrial coating, medicine, agriculture The industry of medicine, organic solvent.Especially because the rapid development of polyamide industry, as preparing among nylon-6 and nylon -66 The demand of the cyclohexanone of body is in the whole world every year all at 1,000,000 tons or more.Now, cyclohexanone production process route mainly has Three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and part of benzene hydrogenation method, and cyclohexane oxidation process is industrial production ring The main process of hexanone, accounts for 90% or more.But this production process is also considered as in all chemical industry process efficiency most Low one.Cyclohexane oxidation synthesizing cyclohexanone process is the key that restrict one of caprolactam production and bottleneck.
Industrially using cyclohexane oxidation production cyclohexanone generally there are three types of method: one is use cobalt salt for catalyst Catalysis oxidation, this method cyclohexane conversion is higher, but due to formed adipic acid cobalt and make reaction kettle be easy fouling, Substantially it is eliminated.Second is that boric acid class catalytic oxidation, this method capital expenditure is high, and energy consumption is high, and technique is extremely complex, operation difficulty Greatly, and equipment and pipeline Severe blockage are easily caused.Third is that this method is effectively kept away with the non-catalyst oxidation of air direct oxidation The problem of having exempted from reaction fouling is industrially widely applied, but the complex process, and intermediate steps are more, cyclohexane conversion Low, hexamethylene internal circulating load is big, and energy consumption is high, and pollution is also larger, especially in cyclohexyl hydroperoxide decomposable process, cyclohexanone Selectivity is poor, and yield is low.In addition, a large amount of spent lyes that the process generates, it is still global environmental protection that processing is difficult so far Problem.
Summary of the invention
The purpose of the present invention is overcoming, the existing method energy consumption for preparing cyclohexanone is high, pollution is big and cyclohexanone selectivity Etc. lower deficiency, a kind of method for preparing cyclohexanone is provided.
The present inventor in the course of the research it was unexpectedly observed that during cyclohexanol prepares cyclohexanone, If introducing portion titanium Si-Al molecular sieve can be mentioned significantly under relatively mild conditions as catalyst in the reaction system The conversion ratio of high cyclohexanol and the selectivity of cyclohexanone.The present invention is completed on this basis.
Therefore, the present invention provides a kind of methods for preparing cyclohexanone, this method comprises: making under oxidation reaction condition Liquid mixture containing hexamethylene alcohol and oxidizing agent flows through catalyst bed；The catalyst bed includes the first catalyst bed Layer and the second catalyst bed, on the basis of the flow direction of liquid mixture, first catalyst bed is located at described the The upstream of two catalyst beds；Wherein, first catalyst bed is filled with Titanium Sieve Molecular Sieve；Second catalyst bed Layer is filled with titanium Si-Al molecular sieve.
By cooperation Titanium Sieve Molecular Sieve and titanium Si-Al molecular sieve as catalyst, even if in the item of mild (energy consumption is lower) Under part, method of the invention can also obtain higher oxidant conversion ratio and cyclohexanone selectivity, even if continuous fortune for a long time Turn, so that the present invention can effectively extend the parallel-adder settle-out time of device, reduces operating cost.In addition, method of the invention In, catalyst is easily recycled, and whole process is environmental-friendly, and it is simple and easy to control, and without especial equipment requirements, it is conducive to industry Metaplasia produces and application.
Particularly, it was found by the inventors of the present invention that will draw off agent be processed into after specific crystallinity again with other raw materials one The titanium silica-alumina catalyst for playing heat treatment and obtaining is used to that oxidant conversion ratio and ring can be further increased in reaction of the invention Hexanone selectivity.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value, these ranges herein Or value should be understood as comprising the value close to these ranges or value.For numberical range, the endpoint value of each range it Between, can be combined with each other between the endpoint value and individual point value of each range, and individually between point value and obtain one Or multiple new numberical ranges, these numberical ranges should be considered as specific open herein.
The method provided by the invention for preparing cyclohexanone includes: to make under oxidation reaction condition containing cyclohexanol and oxidation The liquid mixture of agent flows through catalyst bed；The catalyst bed includes the first catalyst bed and the second catalyst bed Layer, on the basis of the flow direction of liquid mixture, first catalyst bed is located at the upper of second catalyst bed Trip；
Wherein, first catalyst bed is filled with Titanium Sieve Molecular Sieve；Second catalyst bed is filled with titanium silicon Aluminum molecular screen.
With the method for the invention it is preferred to which this method is also when desirable oxidation selectivity of product drops to the condition 1 of satisfaction Including being adjusted step, until stop the set-up procedure when desirable oxidation selectivity of product rises to the condition 2 of satisfaction,
Condition 1, sometime the desirable oxidation selectivity of product S under ttWith initial target oxidation product selectivity S0Ratio Value St/S0For 0.85≤St/S0<1；
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S0Ratio S '/S0For 0.9≤ S’/S0≤1；
The set-up procedure is to improve the mass content of oxidant in the liquid mixture.
According to the method for the present invention, in more preferable condition 1, St/S0<0.9。
According to the method for the present invention, oxidant in the liquid mixture is more preferably improved with 0.02-5%/day amplitude Mass content.
Method according to the invention it is possible to improve the mass content of oxidant in liquid mixture using various methods. Such as: the additive amount of oxidant when preparing the liquid mixture can be improved to improve the matter of oxidant in liquid mixture Measure content.When oxidant is provided in the form of oxidizing agent solution, the concentration of oxidant in raising oxidizing agent solution can be passed through Come realize improve liquid mixture in oxidant mass content, the dosage of oxidizing agent solution can remain unchanged at this time, can also To be accordingly adjusted (for example, reducing the dosage of oxidizing agent solution, accordingly to keep the ratio between cyclohexanol and oxidant It is constant), as long as can ensure that the mass content of oxidant in liquid mixture to improve.This mode is especially suitable for making The occasion of oxidant (such as hydrogen peroxide) is provided to oxidizing agent solution form (such as hydrogen peroxide), it at this time can be by improving oxygen The concentration of oxidant (such as hydrogen peroxide) in agent solution (such as hydrogen peroxide).Oxidant is first in the oxidizing agent solution Beginning concentration can be conventional selection, generally can be 20-70 weight %, preferably 20-50 weight %.
According to the method for the present invention, the Titanium Sieve Molecular Sieve more preferably loaded in first catalyst bed and described the The weight ratio of the titanium Si-Al molecular sieve loaded in two catalyst beds can be 0.1-20:1, preferably 0.2-10:1.
According to the method for the present invention, first catalyst bed and the second catalyst bed can respectively contain one Or multiple catalyst beds.It is more when the first catalyst bed and/or the second catalyst bed contain multiple catalyst beds It can be series connection between a catalyst bed, or be connected in parallel, can also be series connection and combination in parallel, example Such as: multiple catalyst beds are divided into multiple groups, the catalyst bed in every group be connected in series and/or be connected in parallel, each group it Between for be connected in series and/or be connected in parallel.First catalyst bed and second catalyst bed can be set same The different zones of one reactor also can be set in different reactors.
According to the method for the present invention, liquid mixture flows through the apparent of the first catalyst bed and the second catalyst bed Speed can be identical, or different.Preferably, liquid mixture flows through the superficial velocity of the first catalyst bed and is v1, the superficial velocity for flowing through the second catalyst bed is v2, wherein v1< v2, can further extend the list of catalyst in this way Journey service life.It is highly preferred that v2/v1=1-10.It is further preferred that v2/v1=2.5-8.
In the present invention, the superficial velocity refers in the unit time through the liquid mixture of catalyst bed whole process The area of a certain cross section of mass flow (in terms of kg/s) and catalyst bed is (with m2Meter) ratio.Generally, it can incite somebody to action The quality of the liquid mixture of fixed bed reactors is sent into unit time as " by whole catalyst beds in the unit time The mass flow of the liquid mixture of layer ".In the present invention, for apparent speed of the liquid mixture in the first catalyst bed No particular/special requirement is spent, it generally can be in 0.001-200kg/ (m2S) in the range of.
Liquid mixture can be adjusted using various methods in the first catalyst bed and the second catalyst bed Superficial velocity.For example, the superficial velocity of liquid mixture can be adjusted by the cross-sectional area of selecting catalyst bed.Tool Body, the cross-sectional area of first catalyst bed can be made to be greater than the cross-sectional area of second catalyst bed, thus So that v1< v2, it is preferable that v2/v1For 1-10, more preferably make v2/v1For 2.5-8.It is determined according to expected superficial velocity The method of the cross-sectional area of catalyst bed be it is known in those skilled in the art, be no longer described in detail herein.
According to the method for the present invention, when the Titanium Sieve Molecular Sieve loaded in first catalyst bed is urged with described second When the weight ratio of the titanium Si-Al molecular sieve loaded in agent bed is preferably 0.2-10:1, first catalyst bed it is interior The internal diameter of diameter and the second catalyst bed is than being preferably 1-6:1.
According to the method for the present invention, residence time of the liquid mixture in the first catalyst bed is T1, in catalyst Total residence time in bed is T, it is preferable that T1/ T=0.3-0.95.It is highly preferred that T1/ T=0.45-0.86, in this way can The further extended catalyst single trip use service life is obtained, and obtains higher desirable oxidation selectivity of product.
According to the method for the present invention, the temperature of the temperature of first catalyst bed and the catalyst bed can be with It is identical or different.From further increase desirable oxidation selectivity of product and further extend catalyst the single trip use service life Angle set out, the temperature of preferably described first catalyst bed is the temperature higher than second catalyst bed.More preferably The temperature on ground, first catalyst bed is 4-30 DEG C higher than the temperature of second catalyst bed, and preferably 5-15 DEG C.
According to the method for the present invention, when catalyst bed contains the first catalyst bed and the second catalyst bed, root Fresh material can be supplemented between the first catalyst bed and the second catalyst bed according to concrete condition, in the first catalyst When bed and/or the second catalyst bed are multiple catalyst beds, as the case may be can the first catalyst bed it Between and/or the second catalyst bed between fresh cyclohexanol is supplemented into the liquid mixture.Such as: in the first catalyst Fresh ring is supplemented between bed and the second catalyst bed, between the first catalyst bed and/or between the second catalyst bed Hexanol and optional fresh solvent.However, it is desirable to which explanation, determines that liquid mixture when superficial velocity refers to and flows through Whole beds of whole beds (that is, whole process of the first catalyst bed) and the second catalyst bed of the first catalyst bed The liquid mixture of (that is, whole process of the second catalyst bed) is not included between the first catalyst bed, the second catalysis The fresh material introduced between the first catalyst bed and the second catalyst bed between agent bed.
According to the method for the present invention, the catalyst bed can only load molecular sieve, can also be containing molecular sieve and non- Active filler.Inactive filler is loaded in catalyst bed to be adjusted the amount of molecular sieve in catalyst bed, from And the speed of reaction is adjusted.When the catalyst bed contains molecular sieve and inactive filler, in catalyst bed The content of inactive filler can be 5-95 weight %.The inactive filler refers to no to oxidation reaction or does not have substantially The filler of catalytic activity, specific example can include but is not limited to: one of quartz sand, ceramic ring and potsherd or It is a variety of.
The total amount (that is, total amount of the first catalyst bed and the molecular sieve in the second catalyst bed) of molecular sieve can be with It is selected according to the specific treating capacity of system.Generally, with first catalyst bed and second catalyst bed On the basis of the total amount of interior molecular sieve, the weight space velocity of the cyclohexanol can be 0.1-50h-1, preferably 0.2-10h-1。
According to the method for the present invention, the oxidant can for it is common it is various can be by the substance of cyclohexanol.It is excellent Selection of land, the oxidant are peroxide.The peroxide refers to the compound for containing-O-O- key in molecular structure, can be with Selected from hydrogen peroxide, organic peroxide and peracid.The organic peroxide refers to one or two in hydrogen peroxide molecule Substance obtained from a hydrogen atom is replaced by organic group.The peracid refers in molecular structure and contains containing the organic of-O-O- key Oxygen acid.The specific example of the peroxide can include but is not limited to: hydrogen peroxide, tert-butyl hydroperoxide, peroxidating are different Propyl benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, in this way can Further decrease separation costs.The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.
According to the method for the present invention, it is the hydrogen peroxide of 5-70% that the hydrogen peroxide, which is usually with mass percentage concentration, The form of aqueous solution is added in reaction system, such as the aqueous hydrogen peroxide solution of technical grade has 27.5%, 30%, 55% and 70% etc..
The dosage of the oxidant can be selected according to the amount of cyclohexanol.Generally, the cyclohexanol and oxidant Molar ratio can be 0.1-20:1, preferably 0.2-10:1, more preferably 1-5:1.
According to the method for the present invention, the liquid mixture can contain solvent, can also not contain solvent, preferably also Containing at least one solvent, the speed and severe degree of reaction can be preferably controlled in this way.The present invention is for the solvent Type is not particularly limited, and the solvent can either dissolve the mixing of both hexamethylene alcohol and oxidizing agent or promotion to be various, again It is capable of the liquid substance of solubilized target oxidation product.Generally, the solvent can be selected from water, the C in addition to cyclohexanol1-C6's Alcohol, C3-C8Ketone and C2-C6Nitrile.The specific example of the solvent can include but is not limited to: water, methanol, ethyl alcohol, positive third Alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably, the solvent is selected from water and in addition to cyclohexanol C1-C6Alcohol.It is highly preferred that the solvent is methanol and/or water.
The dosage of the solvent is not particularly limited in the present invention, can be carried out according to the amount of hexamethylene alcohol and oxidizing agent Selection.Generally, the weight ratio of the solvent and the cyclohexanol can be 0.1-100:1, preferably 0.2-80:1.
According to the method for the present invention, the oxidation reaction condition can be selected according to the set goal oxidation product. Specifically, the liquid mixture flows through first catalyst bed and the condition of second catalyst bed is respectively wrapped Include: temperature can be 0-80 DEG C, preferably 20-70 DEG C；In terms of gauge pressure, pressure can be 0.1-3MPa.
With the method for the invention it is preferred to further include being sent at least one alkaline matter, institute into the liquid mixture The additive amount for stating alkaline matter is in the liquid mixture pH value in the range of 6-9, can obtain better reaction in this way Effect.It is highly preferred that the additive amount of the alkaline matter makes the pH value of the liquid mixture be in the range of 6.5-8.5 It is interior, preferably 6.8-8.2.In pH value 6.5 or more (or being 7 or more) of the liquid mixture contacted with molecular sieve, such as Fruit uses alkali, further increases the pH value of the liquid mixture, still is able to obtain said effect.The liquid mixture PH value refers in 25 DEG C and the pressure of 1 normal atmosphere, the pH value of the liquid mixture of measurement.
Herein, the alkaline matter refers to that the pH value of its aqueous solution is the substance greater than 7.The tool of the alkaline matter Body example can include but is not limited to: ammonia is (that is, NH3), amine, quaternary ammonium base and M1(OH)n(wherein, M1For alkali metal or alkaline earth gold Belong to, n is and M1The identical integer of chemical valence).
As the alkaline matter, ammonia can be introduced in the form of liquefied ammonia, can also be introduced in form of an aqueous solutions, also It can introduce in gaseous form.The concentration of ammonia (that is, ammonium hydroxide) as aqueous solution form is not particularly limited, and can be normal Rule selection, such as 1-36 weight %.
As the alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the substance to be formed by alkyl, including one Grade amine, secondary amine and tertiary amine.The amine is specifically as follows substance and/or C shown in Formulas I3-C11Heterocyclic amine,
In Formulas I, R1、R2And R3It respectively can be H or C1-C6Alkyl (such as C1-C6Alkyl), and R1、R2And R3It is different When be H.Herein, C1-C6Alkyl include C1-C6Straight chained alkyl and C3-C6Branched alkyl, specific example may include But be not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, Tertiary pentyl, neopentyl and n-hexyl.
The specific example of amine can include but is not limited to: methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, N-propylamine, di-n-propylamine, Tri-n-Propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, Zhong Ding Base amine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, iso-amylamine, Di-iso-amylamine, triisoamylamine, tertiary amylamine, n-hexylamine and n-octyl amine.
The heterocyclic amine is on finger ring with the compound on nitrogen-atoms and the nitrogen-atoms with lone pair electrons.It is described miscellaneous Cyclammonium for example can for substituted or unsubstituted pyrroles, substituted or unsubstituted nafoxidine, substituted or unsubstituted pyridine, It is substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted Quinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, takes substituted or unsubstituted dihydroquinoline Generation or one of unsubstituted isoquinolin and substituted or unsubstituted pyrimidine or a variety of.
As the alkaline matter, quaternary ammonium base is specifically as follows substance shown in Formula Il.The specific reality of the quaternary ammonium base Example can include but is not limited to: tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide (including four n-propyls Ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetrabutylammonium hydroxide (including 4-n-butyl ammonium hydroxide, four sec-butyl hydrogen-oxygens Change ammonium, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As the alkaline matter, M1(OH)nFor the hydroxide of alkali metal or the hydroxide of alkaline-earth metal, such as can Think sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide and calcium hydroxide.
According to the method for the present invention, the alkaline matter can be used directly, the alkaline matter can also be configured to It is used after solution.It is sent into fixed bed reactors after alkaline matter being mixed with oxidant and optionally solvent, it is described Mixing can carry out outside reactor, can also carry out, be not particularly limited in reactor.
With the method for the invention it is preferred to which the alkaline matter is pyridine.
According to the method for the present invention, Titanium Sieve Molecular Sieve is one kind that titanium atom replaces a part of silicon atom in lattice framework The general name of zeolite can use chemical formula xTiO2·SiO2It indicates.The present invention does not have the content of titanium atom in Titanium Sieve Molecular Sieve It is particularly limited to, can be the conventional selection of this field.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more Preferably 0.015-0.025.
Titanium Sieve Molecular Sieve described in first catalyst bed can be different from titanium with various topological structures for common The Titanium Sieve Molecular Sieve of si molecular sieves comprising except all Titanium Sieve Molecular Sieve of Titanium Sieve Molecular Sieve, such as: the Titanium Sieve Molecular Sieve The Titanium Sieve Molecular Sieve (such as TS-1) of MFI structure, the titanium of the Titanium Sieve Molecular Sieve (such as TS-2) of MEL structure, BEA structure can be selected from Si molecular sieves (such as Ti-Beta), the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, the Titanium Sieve Molecular Sieve of MOR structure are (such as Ti-MOR), the Titanium Sieve Molecular Sieve (such as Ti-TUN) of TUN structure, the Titanium Sieve Molecular Sieve of two-dimentional hexagonal structure (such as Ti-MCM-41, ) and the Titanium Sieve Molecular Sieve of other structures (such as Ti-ZSM-48) Ti-SBA-15.Titanium Sieve Molecular Sieve described in second bed is preferred The Titanium Sieve Molecular Sieve of Titanium Sieve Molecular Sieve, MEL structure selected from MFI structure and the Titanium Sieve Molecular Sieve of BEA structure, more preferably MFI The Titanium Sieve Molecular Sieve of structure, preferably TS-1.
The titanium Si-Al molecular sieve refers to that titanium atom and aluminium atom replace a kind of boiling of a part of silicon atom in lattice framework The general name of stone.The titanium Si-Al molecular sieve can be the common titanium Si-Al molecular sieve with various topological structures, such as: institute State titanium Si-Al molecular sieve can for the titanium Si-Al molecular sieve of MFI structure, the titanium Si-Al molecular sieve of MEL structure, BEA structure titanium Si-Al molecular sieve, the titanium Si-Al molecular sieve of MWW structure, the titanium Si-Al molecular sieve of MOR structure, TUN structure titanium silicoaluminophosphate molecular One of titanium Si-Al molecular sieve of sieve, the titanium Si-Al molecular sieve of two-dimentional hexagonal structure and other structures is a variety of.The titanium silicon Aluminum molecular screen is preferably the titanium sial point of the titanium Si-Al molecular sieve of MFI structure, the titanium Si-Al molecular sieve of MEL structure and BEA structure One of son sieve is a variety of, more preferably the titanium Si-Al molecular sieve of MFI structure.
According to the present invention, as long as using titanium Si-Al molecular sieve that the purpose of the present invention can be realized as catalyst, but originally The inventor of invention has found under study for action, will be particularly conducive to improve oxidation using titanium silica-alumina catalyst made from ad hoc approach Agent conversion ratio and cyclohexanone selectivity.
Therefore, a preferred embodiment of the invention A, the titanium Si-Al molecular sieve are made by the following method:
(1) agent will be drawn off to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, separated The first solid for being 70-90% to relative crystallinity, wherein described to draw off agent as using Titanium Sieve Molecular Sieve as catalyst activity The reaction unit of component draws off agent；
(2) is carried out after mixing first solid, silicon source, optional titanium source in the presence of aqueous solvent with alkali source Two heat treatments.Wherein, the titanium source is the ingredient selectively used.
In the preferred embodiment of the present invention A, the reaction unit using Titanium Sieve Molecular Sieve as catalyst activity component The agent that draws off can be to use Titanium Sieve Molecular Sieve to draw off agent, example as what is drawn off in the device of catalyst activity component from various Such as agent can be drawn off for what is drawn off from using Titanium Sieve Molecular Sieve as the oxidation reaction apparatus of catalyst activity component.The oxygen Changing reaction can be various oxidation reactions, such as described using Titanium Sieve Molecular Sieve as the reaction unit of catalyst activity component Draw off agent can for Ammoximation reaction device draw off agent, hydroxylating device draws off agent and epoxidation reaction device One of agent or a variety of is drawn off, be specifically as follows cyclohexanone oxamidinating reaction unit draws off agent, phenol hydroxylation reaction dress Set draw off agent and propylene ring oxidation reaction device draw off one of agent or a variety of, it is preferably described to draw off agent as alkaline ring The catalyst of inactivation is reacted under border, therefore, draws off agent unloading for cyclohexanone oxamidinating reaction unit for the present invention is preferably described Agent out (such as the titanium-silicon molecular sieve TS-1 of inactivation, powdery, partial size is in 100-500nm).
In the preferred embodiment of the present invention A, it is described draw off agent refer to using solvent wash or roast etc. conventional regenerations side Method can not be allowed to activation recovering to initial activity 50% in the case where the catalyst of inactivation (initial activity refers to identical Under reaction condition, average activity of the catalyst within 1h.Such as in the reaction of practical cyclohexanone oximeization, at the beginning of general catalyst Activity will reach 95% or more).
The activity for drawing off agent is different according to its source.Generally, the activity for drawing off agent can be the titanium silicon molecule Sieve the 5-95% of the activity (that is, fresh dose activity) when fresh.Preferably, the activity for drawing off agent can be the titanium silicon point Son sieves active 50% when fresh hereinafter, the activity for further preferably drawing off agent can be the Titanium Sieve Molecular Sieve fresh When active 10-40%.The activity of fresh dose of the Titanium Sieve Molecular Sieve is generally 90% or more, and usually 95% or more.
In the preferred embodiment of the present invention A, it is described draw off agent can from industrial deactivator or in the lab Decaying catalyst after being reacted.Certainly, from the angle of preparation effect, method of the invention can also be using fresh point For son sieve such as Titanium Sieve Molecular Sieve as raw material, only improper for cost control angularly, method provided by the invention is main To turn waste into wealth, using the catalyst containing Titanium Sieve Molecular Sieve of inactivation as raw material to save cost.
In the preferred embodiment of the present invention A, the agent that draws off of each device is respectively surveyed using the reaction of each device Fixed, as long as guaranteeing, in identical device, under identical reaction condition, the activity for drawing off agent is lower than the work of fresh catalyst Property, as of the invention draws off agent.As previously mentioned, the activity for drawing off agent is lower than the activity of fresh catalyst in preferred situation 50%.
In the preferred embodiment of the present invention A, by cyclohexanone oxamidinating reaction unit draw off agent for, the activity It measures by the following method:
Take TS-1 molecular sieve (by " and Zeolites, method described in 1992, Vol.12:943~950 " preparation, TiO2Mass percentage be 2.1%) be placed in slurry bed reactor of the 100mL with continuous feed and membrane separation device, Mixture (the volume of water and hydrogen peroxide of water and the hydrogen peroxide of 30wt% is added under stirring with the speed of 5.7mL/h Than the mixture (volume ratio of cyclohexanone and the tert-butyl alcohol of cyclohexanone and the tert-butyl alcohol being added with the speed of 10.5mL/h for 10:9) For 1:2.5), 36wt% ammonium hydroxide is added with the speed of 5.7mL/h, above-mentioned three strands of materials stream is while being added, while with corresponding Speed continuous discharge, reaction temperature maintain 80 DEG C, after stable reaction every 1h to product sampling gas chromatography to liquid phase Composition analyzed, be calculated using the following equation the conversion ratio of cyclohexanone and the activity as Titanium Sieve Molecular Sieve.Hexamethylene The conversion ratio of ketone=[(mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/cyclohexanone being added rubs You measure] × 100%.Wherein, using the result of 1h as initial activity.
In the preferred embodiment of the present invention A, preferred steps (2) carry out as follows: by silicon source and alkali source aqueous Mixed solution is mixed to get in the presence of solvent, after the mixed solution is mixed with first solid and titanium source described in progress Second heat treatment.It so can be further improved the activity of titanium Si-Al molecular sieve.
In the preferred embodiment of the present invention A, the preferably described mashing carries out at normal temperatures and pressures.
In the preferred embodiment of the present invention A, in the case where no specified otherwise, heat treatment is usually the case where sealing Under carry out at autogenous pressures.
In the preferred embodiment of the present invention A, the temperature of the preferably first heat treatment is 20-45 DEG C of (such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, the arbitrary value between 45 DEG C or above-mentioned numerical value).
In the preferred embodiment of the present invention A, the time of first heat treatment can be determined according to needs, needle To the present invention, the time of the preferably first heat treatment is 1-30h, preferably 1-24h, more preferably 10-20h.Invention of the invention People's discovery can be more advantageous to control crystallinity under specific first heat treatment condition and meet the above range, to be urged Change the titanium Si-Al molecular sieve of excellent performance.
In the preferred embodiment of the present invention A, the temperature of the preferably second heat treatment is 100-200 DEG C, more preferably 120- 180 DEG C, further preferably 140-170 DEG C.
In the preferred embodiment of the present invention A, the time of preferably described second heat treatment can be true according to needing to carry out Fixed, for the present invention, the time of the preferably second heat treatment is 0.5-25h, preferably 2-24h, more preferably 5-20h.
In the preferred embodiment of the present invention A, concentration > 0.1mol/L of the preferably described organic acid soln, more preferably >= 1mol/L, further preferred 2-15mol/L.In the present invention, the primary solvent of the acid solution is water, can also be added according to needs Enter other solvents aids.The catalytic performance for the titanium Si-Al molecular sieve being so prepared is more preferably.
In the preferred embodiment of the present invention A, preferably draw off agent, titanium source, silicon source, Organic Acid and Base source and water mass ratio For 100:(0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), more preferably 100:(0.5-10): (0.5-10): (1-15): (1-20): (100-800), most preferably 100:(1-5): (0.5-2): (2-8): (5-15): (150-250) draws off agent with SiO2Meter, organic acid is with H+Meter, alkali source is with N or OH-Meter.It is highly preferred that drawing off agent and organic acid Mass ratio is 100:(2-8).
In the preferred embodiment of the present invention A, the Titanium Sieve Molecular Sieve can be common with various topological structures Titanium Sieve Molecular Sieve, can be identical or different with the Titanium Sieve Molecular Sieve in the first catalyst bed, such as: the Titanium Sieve Molecular Sieve The Titanium Sieve Molecular Sieve (such as TS-1) of MFI structure, the titanium of the Titanium Sieve Molecular Sieve (such as TS-2) of MEL structure, BEA structure can be selected from Si molecular sieves (such as Ti-Beta), the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, the Titanium Sieve Molecular Sieve of hexagonal structure are (such as Ti-MCM-41, Ti-SBA-15), Titanium Sieve Molecular Sieve (such as Ti- of the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structure, TUN structure ) and one of the Titanium Sieve Molecular Sieve of other structures (such as Ti-ZSM-48) or a variety of TUN.
Preferably, the Titanium Sieve Molecular Sieve be selected from the Titanium Sieve Molecular Sieve of MFI structure, the Titanium Sieve Molecular Sieve of MEL structure and One of Titanium Sieve Molecular Sieve of BEA structure is a variety of.It is highly preferred that the Titanium Sieve Molecular Sieve is the titanium silicon molecule of MFI structure Sieve, such as TS-1 molecular sieve.
In the preferred embodiment of the present invention A, the organic acid is not required particularly, it can having for C1-C10 One of machine carboxylic acid, preferably aphthenic acids, Peracetic acid and Perpropionic Acid are a variety of.It was found by the inventors of the present invention that using Particular types and the organic acid of dosage can be more advantageous to control crystallinity and meet the above range, so that it is good to obtain catalytic performance Titanium Si-Al molecular sieve.
In the preferred embodiment of the present invention A, the titanium source can for organic titanium source (such as organic titanate) and/or Inorganic ti sources (such as inorganic titanium salt).Wherein, inorganic ti sources can be TiCl4、Ti(SO4)2、TiOCl2, titanium hydroxide, oxidation One of titanium, nitric acid titanium salt and phosphoric acid titanium salt etc. are a variety of, and organic titanium source can be in fatty alcohol titanium and organic titanate It is one or more.The titanium source is preferably organic titanium source, further preferably organic titanate.The organic titanate is preferred To be M with structural formula4TiO4Organic titanate, wherein M is preferably to have the alkyl of 1-4 carbon atom, and 4 M can be with Identical or different, it is isopropyl titanate, metatitanic acid n-propyl, butyl titanate and metatitanic acid four that the preferably described organic titanate, which is selected from, One of ethyl ester is a variety of.The specific example of the titanium source can be but be not limited to: TiOCl2, titanium tetrachloride, titanium sulfate, Metatitanic acid orthocarbonate (the various isomers including metatitanic acid orthocarbonate, such as four n-propyl of tetraisopropyl titanate and metatitanic acid), four fourth of metatitanic acid One of ester (the various isomers of butyl titanate, such as tetra-n-butyl titanate) and tetraethyl titanate are a variety of.
In the preferred embodiment of the present invention A, optional wider range of the type of the alkali source can be organic base Source and/or inorganic alkali source, wherein inorganic alkali source can be ammonia or cation is the alkali of alkali or alkaline earth metal, such as can be with For sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide etc., organic alkali source can be urine One of element, aliphatic amine compound, aliphatic alcohol amine compounds and quaternary ammonium alkali cpd are a variety of.
In the preferred embodiment of the present invention A, the quaternary ammonium base can be various organic level Four ammonium alkali, the aliphatic Amine can be various NH3In at least one hydrogen replaced by aliphatic alkyl (preferably alkyl) after the compound that is formed, it is described Aliphatic hydramine can be various NH3In at least one hydrogen by hydroxyl aliphatic alkyl (preferably alkyl) replace after The compound of formation.
Specifically, the quaternary ammonium base can be the quaternary ammonium base as shown in Formula II, and the aliphatic amine can be formula III table The aliphatic amine shown, the aliphatic hydramine can be the aliphatic hydramine such as formula IV expression:
In Formula II, R5、R6、R7And R8Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane Base, such as: R5、R6、R7And R8Respectively can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or Tert-butyl.
R9(NH2)nFormula III
In formula III, n is an integer of 1 or 2.When n is 1, R9For C1~C6Alkyl, including C1~C6Straight chained alkyl and C3-C6Branched alkyl, as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, Neopentyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R9For C1-C6Alkylidene, including C1~C6Straight-chain alkyl-sub and C3~C6Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.It is more excellent Selecting aliphatic amine compound is one of ethamine, n-butylamine, butanediamine and hexamethylene diamine or a variety of.
(HOR10)mNH(3-m)Formula IV
In formula IV, m R10It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3- C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is further preferred that the fat Race's alcohol amine compound is one of monoethanolamine, diethanol amine and triethanolamine or a variety of.
Most preferably, the alkali source is sodium hydroxide, ammonium hydroxide, ethylenediamine, n-butylamine, butanediamine, hexamethylene diamine, monoethanol One of amine, diethanol amine, triethanolamine, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide are a variety of.
Wherein, when containing ammonium hydroxide in the alkali source, the molar ratio of alkali source is to include molecular forms NH3And ionic species NH4 +Existing ammonia meter.
In the preferred embodiment of the present invention A, the preferably described alkali source is provided in the form of aqueous slkali, more preferable aqueous slkali PH > 9.
In the preferred embodiment of the present invention A, source of aluminium is the substance for being capable of providing aluminium, and preferably source of aluminium is aluminium One of colloidal sol, aluminium salt, aluminium hydroxide and aluminium oxide are a variety of, and Aluminum sol preferred content in terms of aluminium oxide is 10-50 weight Measure %.
In the preferred embodiment of the present invention A, the aluminium salt can be inorganic aluminate and/or organic aluminium salt, it is described organic Aluminium salt is preferably the organic aluminium salt of C1-C10, and the inorganic aluminate for example can be aluminum sulfate, sodium metaaluminate, aluminium chloride and nitre One of sour aluminium is a variety of.
In the preferred embodiment of the present invention A, method preferably of the invention further includes the material being heat-treated from step (2) The step of the step of middle recovery product, recovery product is conventional method, is familiar with by those skilled in the art, is had no herein Special requirement, generally refer to the process that product is filtered, washed, dries and roasts.Wherein, described drying process can be in 20- It is carried out at a temperature of between 200 DEG C, described roasting process can be between 300-800 DEG C first in nitrogen atmosphere after 0.5-6h 3-12h is carried out in air atmosphere.
The present inventor is it has furthermore been found that if same after using the Si-Al molecular sieve of inactivation and organic acid etc. to contact Sample can obtain the preferable titanium Si-Al molecular sieve of cyclohexanone catalytic effect, therefore, another kind preferred implementation side according to the present invention Formula B, the method for preparing the titanium Si-Al molecular sieve include:
(a) agent will be drawn off to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, separated The first solid for being 50-70% to relative crystallinity, wherein described to draw off agent as using Si-Al molecular sieve as catalyst activity The reaction unit of component draws off agent；
(b) is carried out after mixing first solid, optional silicon source, titanium source in the presence of aqueous solvent with alkali source Two heat treatments.Wherein, source of aluminium is the ingredient selectively used.
In the preferred embodiment of the present invention B, being specifically defined as previously mentioned, only Titanium Sieve Molecular Sieve is replaced for agent is drawn off For Si-Al molecular sieve.The agent that draws off of the reaction unit using Si-Al molecular sieve as catalyst activity component can be from each Kind use Si-Al molecular sieve as the agent that draws off drawn off in the device of catalyst activity component, such as can be to divide from sial Son sieve draws off the agent (synthetic reaction of such as hydrogen sulfide and methanol as what is drawn off in the synthetic reaction device of catalyst activity component Device draws off agent), or it is unloaded from the catalytic cracking reaction device using Si-Al molecular sieve as catalyst activity component Out draw off agent.It (is such as lost for the preferably described agent that draws off for drawing off the synthetic reaction device that agent is hydrogen sulfide and methanol of the invention Si-Al molecular sieve ZSM-5 living, powdery, partial size is in 100-500nm).
As previously mentioned, the activity for drawing off agent is lower than active the 50% of fresh catalyst in preferred situation.
In the preferred embodiment of the present invention B, by the synthetic reaction device of hydrogen sulfide and methanol draw off agent for, institute Activity is stated to measure by the following method:
By ZSM-5 molecular sieve (by the preparation of method described in comparative example 1 in the CN1235875A) vapor at 200 DEG C Tabletting after processing 10h, sieving take 20-40 mesh particle loaded in the pipe reaction pipe that diameter is 0.8cm, length is 55cm, urge Catalyst particles bed volume is 2cm3.Be 300 DEG C in the temperature of reaction, the pressure of reaction is 1atm, hydrogen sulfide and methanol into Material molar ratio is 1:2, and total gas volume air speed is 700h-1Under conditions of, carry out the catalysis reaction of synthesizing dimethyl thioether.It utilizes The product composition that gas-chromatography obtained after analysis of catalysed reactions every 1 hour, calculates the conversion ratio of methanol simultaneously based on the analysis results As the activity of Si-Al molecular sieve.The conversion ratio of methanol=[(mole-of the methanol of addition unreacted methanol rubs You amount)/be added methanol mole] × 100%.Wherein, using the result of 1h as initial activity.
In the preferred embodiment of the present invention B, preferred steps (b) carry out as follows: by containing alkali source aqueous solution with Second heat treatment is carried out after first solid and titanium source mixing.
In the preferred embodiment of the present invention B, the temperature of the preferably first heat treatment is 50-150 DEG C.
In the preferred embodiment of the present invention B, the time of first heat treatment can be determined according to needs, needle To the present invention, the time of the preferably first heat treatment is 0.5-40h, preferably 1-24h, more preferably 10-20h.Hair of the invention Bright people's discovery can be more advantageous to control crystallinity under specific first heat treatment condition and meet the above range, to obtain The good titanium Si-Al molecular sieve of catalytic performance.
In the preferred embodiment of the present invention B, the temperature of the preferably second heat treatment is 100-200 DEG C, more preferably 120- 180 DEG C, further preferably 140-170 DEG C.
In the preferred embodiment of the present invention B, the time of preferably described second heat treatment can be true according to needing to carry out Fixed, for the present invention, the time of the preferably second heat treatment is 0.5-25h, preferably 2-24h, more preferably 5-20h.
In the preferred embodiment of the present invention B, the mass ratio for preferably drawing off agent, titanium source, Organic Acid and Base source and water is 100:(0.1-10): (0.005-50): (0.5-50): (20-1000), more preferably 100:(0.5-10): (1-15): (1- 20): (100-800), most preferably 100:(1-5): (2-8): (5-15): (150-250).Agent is drawn off with SiO2Meter, organic acid With H+Meter, alkali source is with N or OH-Meter.It is highly preferred that the mass ratio for drawing off agent and organic acid is 100:(2-8).
In the preferred embodiment of the present invention B, the Si-Al molecular sieve can be common with various topological structures Si-Al molecular sieve, it is preferable that the silicoaluminophosphate molecular is screened from the Si-Al molecular sieve of MFI structure, the Si-Al molecular sieve of MEL structure At least one of with the Si-Al molecular sieve of BEA structure.It is highly preferred that the Si-Al molecular sieve is the silicoaluminophosphate molecular of MFI structure Sieve, such as ZSM-5 molecular sieve.
For the condition of mashing, organic acid soln, titanium source, the specific choice of alkali source etc. can be with preferred embodiment A In it is identical (as previously described), details are not described herein.
As described above, the invention further relates to the method for preparing titanium Si-Al molecular sieve, specific steps such as embodiment A or reality It applies described in mode B.Prepared titanium Si-Al molecular sieve is conducive to the diffusion of reactants and products molecule in catalysis reaction, The catalytic oxidation participated in alcohol (such as tert-butyl alcohol or cyclohexanol) is particularly advantageous.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, used reagent is commercially available chemically pure reagent.
In following embodiment and comparative example, if not otherwise specified, pressure is gauge pressure.
In following embodiment and comparative example, the composition of each ingredient in the reaction solution that is measured using gas chromatography is led to Overcorrect normalization method is quantified, and following formula is respectively adopted on this basis and calculates oxidant conversion ratio and cyclohexanone selection Property:
Oxidant conversion ratio (%)=(molal quantity for participating in molal quantity/addition oxidant of the oxidant of reaction) × 100；
Oxidant effective rate of utilization (%)=(molal quantity of molal quantity/addition oxidant of cyclohexanone) × 100；
Cyclohexanone selectivity (%)=(molal quantity of the molal quantity of cyclohexanone/reaction consumption cyclohexanol) × 100.
In following embodiment and comparative example, preformed catalyst used the preparation method is as follows: in normal pressure and 60 DEG C of conditions Under, first organo-silicon compound ethyl orthosilicate is added in tetrapropylammonium hydroxide solution and is mixed, stirring hydrolysis 5h is obtained Colloidal solution；Then Titanium Sieve Molecular Sieve or titanium Si-Al molecular sieve are added to be uniformly mixed among above-mentioned gained colloidal solution and are obtained Slurries, and the wherein mass ratio of Titanium Sieve Molecular Sieve or titanium Si-Al molecular sieve, silanes, tetrapropylammonium hydroxide and water For 100:25:5:250；Above-mentioned slurries are continued after stirring 2h, roasting after conventional mist projection granulating can be obtained used in the present invention Microballoon shape catalyst.
Preparation example 1
A prepares titanium Si-Al molecular sieve in preferred embodiments
(1) take TS-1 molecular sieve (by " and Zeolites, method described in 1992, Vol.12:943~950 " preparation, TiO2Mass percentage be 2.1%) be placed in 100mL band continuous feed and membrane separation device slurry bed reactor in, stirring Mix the mixture (volume ratio of water and hydrogen peroxide that water and the hydrogen peroxide of 30wt% is added under state with the speed of 5.7mL/h For 10:9), the mixture of cyclohexanone and the tert-butyl alcohol is added with the speed of 10.5mL/h, and (volume ratio of cyclohexanone and the tert-butyl alcohol is 1:2.5), 36wt% ammonium hydroxide is added with the speed of 5.7mL/h, above-mentioned three strands of materials stream is while being added, while with corresponding speed Spend continuous discharge, reaction temperature maintains 80 DEG C, after stable reaction every 1h to product sampling gas chromatography to liquid phase Composition is analyzed, and the conversion ratio of cyclohexanone and the activity as Titanium Sieve Molecular Sieve are calculated using the following equation.Hexamethylene The conversion ratio of ketone=[(mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/cyclohexanone being added rubs You measure] × 100%.The yclohexanone conversion ratio for being for the first time 1h measurement is its initial activity, value 99.5%.By one Section time about 168h uses roasting regeneration after isolating catalyst after yclohexanone conversion ratio drops to 50% by initial 99.5% Mode regenerates and (roasts 4h in air atmosphere at 570 DEG C), then proceed to for cyclohexanone oxamidinating reaction in, repeatedly into The step for row, until the activity after regeneration is lower than the 50% of initial activity, the ammonia deuteration catalyst sample conduct at this moment inactivated Of the invention draws off agent, successively obtains drawing off agent SH-1 (activity is 40%), SH-2 (activity is 25%) according to preceding method, SH-3 (activity is 10%).
(2) under room temperature (20 DEG C, similarly hereinafter) normal pressure (0.1MPa, similarly hereinafter), first by the cyclohexanone oximate catalyst of inactivation The cycloalkanes aqueous acid of SH-1 and 1mol/L is mixed with beating, and mixed serum is then mixed to processing 12h at 45 DEG C；Gu By solid (relative crystallinity 71%), silicon source aluminum sulfate, titanium source titanium sulfate and sodium hydrate aqueous solution, (pH is after liquid separation 12) mixed liquor is put into stainless steel sealing reaction kettle after mixing, handles 12h at 170 DEG C, wherein quality of material group, which becomes, to be lost Cyclohexanone oximate catalyst living: titanium source: silicon source: acid: alkali: the cyclohexanone oximate of water=100:1:1:2:5:250, inactivation is urged Agent is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.It by products therefrom filtering, is washed with water, and in 110 DEG C of drying 120min, Then in 550 DEG C of roasting temperature 3h, molecular sieve is obtained, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure Molecular sieve (TS-A).
(3) at normal temperatures and pressures, first by the peracetic acid soln of cyclohexanone oximate the catalyst SH-2 and 5mol/L of inactivation It is mixed with beating, mixed serum is then mixed to processing 20h at 20 DEG C；By solid, (relative crystallinity is after separation of solid and liquid 89%), (pH is for silicon source Aluminum sol (content be 20 weight %), titanium source butyl titanate and tetrapropylammonium hydroxide solution 10) mixed liquor is put into stainless steel sealing reaction kettle after mixing, 20h is handled at 150 DEG C, wherein quality of material group, which becomes, loses Cyclohexanone oximate catalyst living: titanium source: silicon source: acid: alkali: water=100:2:0.5:8:15:200, the cyclohexanone oximate of inactivation Catalyst is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then according to the method recovery product of step (2), titanium sial point is obtained Son sieve, XRD crystalline phase figure show to have obtained the titanium Si-Al molecular sieve (TS-B) with MFI structure.
(4) at normal temperatures and pressures, by the Perpropionic Acid aqueous solution of cyclohexanone oximate the catalyst SH-3 and 8mol/L of inactivation It is mixed with beating, mixed serum is then mixed to processing 10h at 30 DEG C；By solid, (relative crystallinity is after separation of solid and liquid 80%), mixed liquor is put into stainless by silicon source aluminium hydroxide, titanium source titanium tetrachloride after mixing with ethylenediamine solution (pH 11) Steel seals reaction kettle, the hydro-thermal process 5h at 140 DEG C, wherein quality of material group becomes the cyclohexanone oximate catalyst of inactivation: Titanium source: silicon source: acid: alkali: water=100:5:2:5:5:150, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, Alkali is in terms of N.Then according to the method recovery product of step (2), titanium Si-Al molecular sieve is obtained, XRD crystalline phase figure shows to obtain Titanium Si-Al molecular sieve (TS-C) with MFI structure.
(5) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, mixed serum is mixed at 60 DEG C It closes, the relative crystallinity of solid is that 65%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure point after separation of solid and liquid Son sieve (TS-D).
(6) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, mixed serum is mixed at 180 DEG C It closes, the relative crystallinity of solid is that 95%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure point after separation of solid and liquid Son sieve (TS-E).
(7) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, Perpropionic Acid aqueous solution is replaced with Formic acid, the relative crystallinity of solid is that 60%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure after separation of solid and liquid Molecular sieve (TS-F).
(8) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the cyclohexanone oximate catalysis of inactivation Agent: acid=100:15, the relative crystallinity of solid is that 62%, XRD crystalline phase figure shows to have obtained and has MFI knot after separation of solid and liquid The titanium Si-Al molecular sieve (TS-G) of structure.
(9) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, mixed serum is mixed at 160 DEG C Conjunction, replaces with acetic acid for Perpropionic Acid aqueous solution, the cyclohexanone oximate catalyst of inactivation: acid=100:10, solid after separation of solid and liquid The relative crystallinity of body is that 55%, XRD crystalline phase figure shows to have obtained the titanium Si-Al molecular sieve (TS-H) with MFI structure.
(10) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, it is directly that TS-1 molecular sieve is (opposite Crystallinity be 100%), silicon source aluminium hydroxide, titanium source titanium tetrachloride mixed with ethylenediamine solution, XRD crystalline phase figure shows to obtain Titanium Si-Al molecular sieve (TS-I) with MFI structure.
Wherein, X-ray diffraction (XRD) crystalline phase figure of sample carries out on Siemens D5005 type x-ray diffractometer Measurement, with sample and authentic specimen in the sum of the diffracted intensity (peak height) that 2 θ are the five fingers diffractive features peak between 22.5 ° -25.0 ° Ratio indicate crystallinity of the sample relative to authentic specimen, here using fresh TS-1 sieve sample as benchmark sample, Crystallinity is calculated as 100%.
Preparation example 2
B prepares titanium Si-Al molecular sieve in preferred embodiments
(1) ZSM-5 molecular sieve (preparing by method described in comparative example 1 in CN1235875A) is lauched steaming at 200 DEG C Tabletting after gas disposal 10h, sieving take 20-40 mesh particle to be loaded in the pipe reaction pipe that diameter is 0.8cm, length is 55cm, Catalyst granules bed volume is 2.0cm3.It is 300 DEG C in the temperature of reaction, the pressure of reaction is 1atm, hydrogen sulfide and methanol Raw materials components mole ratio be 1:2, total gas volume air speed be 700h-1Under conditions of, the catalysis for carrying out synthesizing dimethyl thioether is anti- It answers.It is formed using the product that gas-chromatography obtained after analysis of catalysed reactions every 1 hour, calculates methanol based on the analysis results Conversion ratio and activity as Si-Al molecular sieve at this time.The conversion ratio of methanol=[(mole-of the methanol of addition is not anti- The mole for the methanol answered)/be added methanol mole] × 100%.Wherein, using the result of 1h as initial activity, Its value is 99%.Through about 180h after a period of time, after methanol conversion drops to 50% by initial 99%, catalysis is isolated It is regenerated with roasting regeneration mode after agent and (is roasted 4h in air atmosphere at 570 DEG C), then proceeded to for hydrogen sulfide and methanol Synthetic reaction in, the step for being repeated, until regeneration after activity be lower than initial activity 50%, at this moment inactivate Catalyst sample draws off agent as of the invention, successively obtains drawing off agent SH-I (activity is 45%), SH- according to preceding method II (activity is 35%), SH-III (activity is 15%).
(2) under room temperature (20 DEG C, similarly hereinafter) normal pressure (0.1MPa, similarly hereinafter), first by the catalyst SH-I and 1mol/L of inactivation Cycloalkanes aqueous acid be mixed with beating, then mixed serum is mixed at 50 DEG C processing 12h；It will consolidate after separation of solid and liquid Mixed liquor is put into not by body (relative crystallinity 70%), titanium source titanium sulfate after mixing with sodium hydrate aqueous solution (pH 12) The steel that becomes rusty seals reaction kettle, handles 12h at 170 DEG C, wherein quality of material group becomes the catalyst of inactivation: titanium source: acid: alkali: Water=100:1:2:5:250, the catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.By products therefrom filtering, use water Washing, and in 110 DEG C of drying 120min, then in 550 DEG C of roasting temperature 3h, molecular sieve is obtained, XRD crystalline phase figure is shown The titanium Si-Al molecular sieve (SA-A) with MFI structure is obtained.
(3) at normal temperatures and pressures, first the peracetic acid soln of the catalyst SH-II and 5mol/L of inactivation are mixed with beating, Mixed serum is then mixed to processing 20h at 150 DEG C；By solid (relative crystallinity 53%), titanium after separation of solid and liquid Mixed liquor is put into stainless steel sealing after mixing with tetrapropylammonium hydroxide solution (pH 10) and reacted by source butyl titanate Kettle handles 20h at 150 DEG C, and wherein quality of material group becomes the catalyst of inactivation: titanium source: acid: alkali: water=100:2:8: 15:200, the cyclohexanone oximate catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is with OH-Meter.Then according to the side of step (2) Method recovery product, obtains titanium Si-Al molecular sieve, and XRD crystalline phase figure shows to have obtained the titanium Si-Al molecular sieve with MFI structure (SA-B)。
(4) at normal temperatures and pressures, the catalyst SH-III of inactivation is mixed with the Perpropionic Acid aqueous solution of 8mol/L and is beaten Processing 10h is then mixed in mixed serum by slurry at 100 DEG C；By solid, (relative crystallinity is after separation of solid and liquid 61%) mixed liquor is put into stainless steel sealing reaction kettle after, titanium source titanium tetrachloride is mixed with ethylenediamine solution (pH 11), The hydro-thermal process 5h at 140 DEG C, wherein quality of material group becomes the catalyst of inactivation: titanium source: acid: alkali: water=100:5:5: 5:150, the catalyst of inactivation is with SiO2Meter, acid is with H+Meter, alkali is in terms of N.Then it according to the method recovery product of step (2), obtains Titanium Si-Al molecular sieve is obtained, XRD crystalline phase figure shows to have obtained the titanium Si-Al molecular sieve (SA-C) with MFI structure.
(5) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, mixed serum is mixed at 40 DEG C It closes, the relative crystallinity of solid is that 41%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure point after separation of solid and liquid Son sieve (SA-D).
(6) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, mixed serum is mixed at 180 DEG C It closes, the relative crystallinity of solid is that 80%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure point after separation of solid and liquid Son sieve (SA-E).
(7) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, Perpropionic Acid aqueous solution is replaced with Formic acid, the relative crystallinity of solid is that 38%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure after separation of solid and liquid Molecular sieve (SA-F).
(8) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, the catalyst of inactivation: acid=100: 15, the relative crystallinity of solid is that 40%, XRD crystalline phase figure shows to have obtained the titanium sial with MFI structure point after separation of solid and liquid Son sieve (SA-G).
(9) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, mixed serum is mixed at 160 DEG C Conjunction, replaces with acetic acid for Perpropionic Acid aqueous solution, the catalyst of inactivation: acid=100:10, the opposite knot of solid after separation of solid and liquid Brilliant degree is that 30%, XRD crystalline phase figure shows to have obtained the titanium Si-Al molecular sieve (SA-H) with MFI structure.
(10) titanium Si-Al molecular sieve is prepared according to the method for step (4), unlike, directly by ZSM-5 molecular sieve (phase To crystallinity be 100%), titanium source titanium tetrachloride mix with ethylenediamine solution, XRD crystalline phase figure shows to have obtained and tie with MFI The titanium Si-Al molecular sieve (SA-I) of structure.
Wherein, X-ray diffraction (XRD) crystalline phase figure of sample carries out on Siemens D5005 type x-ray diffractometer Measurement, with sample and authentic specimen in the sum of the diffracted intensity (peak height) that 2 θ are the five fingers diffractive features peak between 22.5 ° -25.0 ° Ratio indicate crystallinity of the sample relative to authentic specimen, here using fresh ZSM-5 molecular sieve sample as benchmark sample, Its crystallinity is calculated as 100%.
Embodiment 1
It reacts and is carried out in the micro fixed-bed reactor being connected in series at two, wherein load one in each reactor Cross section is circular isometrical catalyst bed, first reaction on the basis of the flow direction of liquid material, positioned at upstream The internal diameter of the first catalyst bed in device and the internal diameter of the second catalyst bed in second reactor for being located at downstream Ratio is 2:1, and (volume average particle size is that 500 μm of spherical shape is urged to filling molding titanium-silicon molecular sieve TS-1 in the first catalyst bed Agent, density 0.76g/cm3), filling molding titanium Si-Al molecular sieve TS-A in the second catalyst bed, Titanium Sieve Molecular Sieve with The weight ratio of titanium Si-Al molecular sieve is 6:1.
By cyclohexanol, as the hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) of oxidant and as molten The methanol of agent is sent into from the bottom of first reactor, by the first catalyst bed with be loaded on molding titanium silicon therein Molecular sieve contacts (superficial velocity v1For 6kg/ (m2S), residence time 0.28h)；The liquid exported from first reactor Mixture then continuously enters in second reactor, by the second catalyst bed with be loaded on molding titanium silicon therein Aluminum molecular screen contacts (superficial velocity v2For 15kg/ (m2S), residence time 0.32h).
Wherein, the molar ratio of cyclohexanol and hydrogen peroxide is 1.2:1, in first reactor and second reactor PH value is 6.8, and pH adjusting agent is ammonium hydroxide (concentration is 25 weight %), and the weight ratio of solvent and cyclohexanol is 15:1；By Temperature in one catalyst bed and the second catalyst bed is controlled as 60 DEG C, 55 DEG C, first reactor and second Pressure in reactor is respectively 1.5MPa；With the total amount of the molecular sieve in the first catalyst bed and the second catalyst bed On the basis of, the weight space velocity of cyclohexanol is 5h-1。
The composition that the reaction mixture exported from reactor is continuously monitored in reaction process, in cyclohexanone selectivity St With initial while proceeding to 0.5 hour (react sampling and measuring) cyclohexanone selectivity S0Ratio St/S0For 0.85≤St/S0<0.9 When (that is, when the condition 1 of satisfaction), the mass content of hydrogen peroxide in liquid mixture is improved (only with 0.02-5%/day amplitude Improved by the concentration of hydrogen peroxide improved in hydrogen peroxide, the dosage of hydrogen peroxide remains unchanged) until cyclohexanone selectivity S ' with Initial cyclohexanone selectivity S0Ratio S '/S0For 0.9≤S '/S0When≤1 (that is, when the condition 2 of satisfaction), stop improving oxidant Mass content.
Continuous operation under the above conditions in operational process, detects the reaction mixture exported from second reactor Composition, and calculate oxidant conversion ratio and cyclohexanone selectivity, wherein the knot when reaction time is 2 hours and 720 hours Fruit is listed in table 1.
Comparative example 1
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the second catalyst bed In the molding titanium-silicon molecular sieve TS-1 of molding titanium Si-Al molecular sieve equivalent replace.
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Comparative example 2
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the first catalyst bed In the molding titanium Si-Al molecular sieve TS-A of molding Titanium Sieve Molecular Sieve equivalent replace.
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Comparative example 3
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the first catalyst bed In the molding titanium Si-Al molecular sieve TS-A of molding Titanium Sieve Molecular Sieve equivalent replace, the molding titanium in the second catalyst bed The molding titanium-silicon molecular sieve TS-1 of Si-Al molecular sieve equivalent replaces.
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Comparative example 4
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the second catalyst bed In the molding Titanium Sieve Molecular Sieve ZSM-5 of molding titanium Si-Al molecular sieve equivalent replace.
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Comparative example 5
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the second catalyst bed In molding titanium Si-Al molecular sieve equivalent the hollow Titanium Sieve Molecular Sieve of molding (hollow Titanium Sieve Molecular Sieve used be purchased from lake The trade mark of Nan Jian feldspathization limited liability company is the hollow Titanium Sieve Molecular Sieve of HTS, and titanium oxide content is 2.5 weight %, under It replaces together).
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Comparative example 6
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the first catalyst bed In the hollow Titanium Sieve Molecular Sieve of molding of molding Titanium Sieve Molecular Sieve equivalent replace.
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Embodiment 2
It reacts and is carried out in the micro fixed-bed reactor being connected in series at two, wherein load one in each reactor Cross section is circular isometrical catalyst bed, first reaction on the basis of the flow direction of liquid material, positioned at upstream The internal diameter of the first catalyst bed in device and the internal diameter of the second catalyst bed in second reactor for being located at downstream Ratio is 6:1, and filling molding Titanium Sieve Molecular Sieve Ti-MCM-41 (exists according to Corma etc. in the first catalyst bed Chem.Commun., prepared by method described in 1994,147-148, and in terms of oxide, the titanium of the Titanium Sieve Molecular Sieve contains Amount is 3 weight %, the spheric catalyst that volume average particle size is 500 μm, density 0.61g/cm3), the second catalyst bed The weight ratio of middle filling molding titanium Si-Al molecular sieve TS-B, Titanium Sieve Molecular Sieve and titanium Si-Al molecular sieve is 10:1.
By cyclohexanol, as the hydrogen peroxide (in the form of the hydrogen peroxide of 30 weight % provide) of oxidant and as molten The methanol of agent is sent into from the bottom of first reactor, by the first catalyst bed with be loaded on molding titanium silicon therein Molecular sieve contacts (superficial velocity v1For 4kg/ (m2S), residence time 0.3h)；The liquid exported from first reactor is mixed Close object then continuously enter in second reactor, by the second catalyst bed with be loaded on molding titanium sial therein divide Son sieve contact (superficial velocity v2For 26kg/ (m2S), residence time 0.05h).
Wherein, the molar ratio of cyclohexanol and hydrogen peroxide is 4:1, the pH in first reactor and second reactor Value is 7.2, and pH adjusting agent is pyridine solution (concentration is 25 weight %), and the weight ratio of solvent and cyclohexanol is 1:1； Temperature in first catalyst bed and the second catalyst bed is controlled as 65 DEG C, 50 DEG C, first reactor and Pressure in two reactors is respectively 0.5MPa；With the molecular sieve in the first catalyst bed and the second catalyst bed On the basis of total amount, the weight space velocity of cyclohexanol is 6h-1。
The composition that the reaction mixture exported from reactor is continuously monitored in reaction process, in cyclohexanone selectivity St With initial while proceeding to 0.5 hour (react sampling and measuring) cyclohexanone selectivity S0Ratio St/S0For 0.85≤St/S0<0.9 When (that is, when the condition 1 of satisfaction), the mass content of hydrogen peroxide in liquid mixture is improved (only with 0.02-5%/day amplitude Improved by the concentration of hydrogen peroxide improved in hydrogen peroxide, the dosage of hydrogen peroxide remains unchanged) until cyclohexanone selectivity S ' with Initial cyclohexanone selectivity S0Ratio S '/S0For 0.9≤S '/S0When≤1 (that is, when the condition 2 of satisfaction), stop improving oxidant Mass content.
Continuous operation under the above conditions in operational process, detects the reaction mixture exported from second reactor Composition, and calculate oxidant conversion ratio and cyclohexanone selectivity, wherein the knot when reaction time is 2 hours and 720 hours Fruit is listed in table 1.
Embodiment 3
Cyclohexanone is prepared using method oxidation cyclohexanol same as Example 1, unlike, the second catalyst bed In the molding titanium Si-Al molecular sieve TS-C of molding titanium Si-Al molecular sieve equivalent replace.
Result when reaction time is 2 hours and 720 hours is listed in table 1.
Embodiment 4-9
Cyclohexanone is prepared according to the method oxidation cyclohexanol of embodiment 3, unlike, respectively by the second catalyst bed In molding titanium Si-Al molecular sieve replace with molding titanium Si-Al molecular sieve TS-D, TS-E, TS-F, TS-G, TS-H and TS-I, instead Answering 2 hours and 720 hours, the results are shown in Table 1.
Embodiment 10
Oxidation cyclohexanol prepares cyclohexanone according to the method for embodiment 1, unlike, it will be in the second catalyst bed Molding titanium Si-Al molecular sieve replaces with molding titanium Si-Al molecular sieve SA-A, result such as 1 institute of table of reaction 2 hours and 720 hours Show.
Embodiment 11
Cyclohexanone is prepared according to the method oxidation cyclohexanol of embodiment 2, unlike, it will be in the second catalyst bed Molding titanium Si-Al molecular sieve replaces with molding titanium Si-Al molecular sieve SA-B, result such as 1 institute of table of reaction 2 hours and 720 hours Show.
Embodiment 12
Cyclohexanone is prepared according to the method oxidation cyclohexanol of embodiment 3, unlike, it will be in the second catalyst bed Molding titanium Si-Al molecular sieve replaces with molding titanium Si-Al molecular sieve SA-C, result such as 1 institute of table of reaction 2 hours and 720 hours Show.
Embodiment 13-18
Cyclohexanone is prepared according to the method oxidation cyclohexanol of embodiment 3, unlike, respectively in the second catalyst bed Molding titanium Si-Al molecular sieve replace with molding titanium Si-Al molecular sieve SA-D, SA-E, SA-F, SA-G, SA-H and SA-I, reaction 2 Hour and the results are shown in Table 1 within 720 hours.
Embodiment 19
Oxidation cyclohexanol prepares cyclohexanone according to the method for embodiment 1, unlike, with the example 1 of CN102616805A In the source of titanium Si-Al molecular sieve obtained as the molding titanium Si-Al molecular sieve in the second catalyst bed, reaction 2 hours and The results are shown in Table 1 within 720 hours.
Embodiment 20
Oxidation cyclohexanol prepares cyclohexanone according to the method for embodiment 1, unlike, the first catalyst bed and second Temperature in catalyst bed is controlled as 60 DEG C, 60 DEG C, and the results are shown in Table 1 within 2 hours and 720 hours for reaction.
Embodiment 21
Oxidation cyclohexanol prepares cyclohexanone according to the method for embodiment 1, unlike, the first catalyst bed and second Temperature in catalyst bed is controlled as 55 DEG C, 60 DEG C, and the results are shown in Table 1 within 2 hours and 720 hours for reaction.
Embodiment 22
Oxidation cyclohexanol prepares cyclohexanone according to the method for embodiment 1, unlike, the first catalyst bed and second Temperature in catalyst bed is controlled as 90 DEG C, 55 DEG C, and the results are shown in Table 1 within 2 hours and 720 hours for reaction.
Table 1
Result above confirms that Titanium Sieve Molecular Sieve and titanium Si-Al molecular sieve are used as by method of the invention to be prepared by cyclohexanol The catalyst of cyclohexanone can also obtain high oxidant even if being reacted under relatively mild reaction condition (energy consumption is lower) Conversion ratio and cyclohexanone selectivity.
And from embodiment 3 and embodiment 4-9, (or the result of embodiment 12 and embodiment 13-18) can be seen that and will draw off Agent is processed into the titanium sial point that specific crystallinity is heat-treated together with other raw materials again later and is obtained in preferred embodiments Son sieve can further increase oxidant conversion ratio and cyclohexanone selectivity.In addition, the result of comparing embodiment 1,10 and 19 can To find out, the catalytic performance of titanium Si-Al molecular sieve made from preferred embodiment is more preferably according to the present invention.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.Of the invention , can be with various simple variants of the technical solution of the present invention are made in range of the technology design, including each technical characteristic is with any Other suitable methods are combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, are belonged to In protection scope of the present invention.

Claims (12)

1. a kind of method for preparing cyclohexanone, this method comprises: making under oxidation reaction condition containing hexamethylene alcohol and oxidizing agent Liquid mixture flows through catalyst bed；The catalyst bed includes the first catalyst bed and the second catalyst bed, with On the basis of the flow direction of liquid mixture, first catalyst bed is located at the upstream of second catalyst bed；
Wherein, first catalyst bed is filled with Titanium Sieve Molecular Sieve；Second catalyst bed is filled with titanium sial point Son sieve.
2. according to the method described in claim 1, wherein, the Titanium Sieve Molecular Sieve of the first catalyst bed filling and described the The weight ratio of the titanium Si-Al molecular sieve of two catalyst beds filling is 0.1-20:1, preferably 0.2-10:1.
3. method according to claim 1 or 2, wherein the liquid mixture flows through the apparent of the first catalyst bed Speed is v1, the superficial velocity for flowing through the second catalyst bed is v2, v1< v2；Preferably, v2/v1=1-10；Further preferably Ground, v2/v1=2.5-8.
4. method according to claim 1 or 2, wherein stop of the liquid mixture in the first catalyst bed Time is T1, the total residence time in catalyst bed is T, T1/ T=0.3-0.95；Preferably, T1/ T=0.45-0.86.
5. method according to claim 1 or 2, wherein the temperature of first catalyst bed is higher than described second and urges The temperature of agent bed；Preferably, the temperature of first catalyst bed is 4- higher than the temperature of second catalyst bed 30℃。
6. method according to claim 1 or 2, wherein the oxidant is peroxide.
7. method according to claim 1 or 2, wherein the molar ratio of cyclohexanol and oxidant is 0.1-20:1, preferably 0.2-10:1.
8. method according to claim 1 or 2, wherein the liquid mixture flow through first catalyst bed and The condition of second catalyst bed respectively includes: that temperature is 0-80 DEG C；In terms of gauge pressure, pressure 0.1-3MPa；With described On the basis of the total amount of first catalyst bed and the molecular sieve in second catalyst bed, the weight space velocity of the cyclohexanol For 0.1-50h-1。
9. according to the method described in claim 1, wherein, the method further includes preparing the step of the titanium Si-Al molecular sieve Suddenly, comprising:
(1) agent will be drawn off to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, it is isolated opposite Crystallinity is the first solid of 70-90%, wherein described to draw off agent as using Titanium Sieve Molecular Sieve as the anti-of catalyst activity component That answers device draws off agent；
(2) it is carried out at the second heat after mixing first solid, silicon source, optional titanium source in the presence of aqueous solvent with alkali source Reason.
10. according to the method described in claim 9, wherein, the reaction using Titanium Sieve Molecular Sieve as catalyst activity component The agent that draws off of device draws off agent for Ammoximation reaction device；
And/or step (2) carries out as follows: silicon source and alkali source are mixed to get mixed solution in the presence of aqueous solvent, Second heat treatment is carried out after the mixed solution is mixed with first solid and titanium source；
And/or first heat treatment temperature be 20-45 DEG C；The temperature of second heat treatment is 100-200 DEG C；
And/or first heat treatment time be 1-30h；The time of second heat treatment is 0.5-25h；
And/or concentration > 0.1mol/L of the organic acid soln；Draw off agent: titanium source: silicon source: organic acid: alkali source: the quality of water Than for 100:(0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000) draws off agent with SiO2Meter, organic acid With H+Meter, alkali source is with N or OH-Meter；
And/or the Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure, the activity for drawing off agent is the catalyst new Active 50% or less when fresh；
And/or the organic acid is one of aphthenic acids, Peracetic acid and Perpropionic Acid or a variety of；The alkali source is ammonia, rouge One of fat race amine, aliphatic hydramine and quaternary ammonium base are a variety of；Source of aluminium is Aluminum sol, aluminium salt, aluminium hydroxide and oxidation One of aluminium is a variety of；The titanium source is selected from inorganic titanium salt and/or organic titanate.
11. according to the method described in claim 1, wherein, the method further includes preparing the titanium Si-Al molecular sieve Step, comprising:
(a) agent will be drawn off to be mixed with beating with organic acid soln, and obtained slurries is subjected to the first heat treatment, it is isolated opposite Crystallinity is the first solid of 50-70%, wherein described to draw off agent as using Si-Al molecular sieve as the anti-of catalyst activity component That answers device draws off agent；
(b) it is carried out at the second heat after mixing first solid, optional silicon source, titanium source in the presence of aqueous solvent with alkali source Reason.
12. according to the method for claim 11, wherein the reaction using Si-Al molecular sieve as catalyst activity component The agent that draws off of device draws off agent for the synthetic reaction device of hydrogen sulfide and methanol；
And/or step (b) carries out as follows: the aqueous solution containing alkali source being mixed with first solid and titanium source laggard Row second heat treatment；
And/or first heat treatment temperature be 50-150 DEG C；The temperature of second heat treatment is 100-200 DEG C；
And/or first heat treatment time be 0.5-40h；The time of second heat treatment is 0.5-25h；
And/or concentration > 0.1mol/L of the organic acid soln；Draw off agent: titanium source: organic acid: alkali source: the mass ratio of water is 100:(0.1-10): (0.005-50): (0.5-50): (20-1000) draws off agent with SiO2Meter, organic acid is with H+Meter, alkali source is with N Or OH-Meter；
And/or the Si-Al molecular sieve is the Si-Al molecular sieve of MFI structure, the activity for drawing off agent is the catalyst new Active 50% or less when fresh；
And/or the organic acid is one of aphthenic acids, Peracetic acid and Perpropionic Acid or a variety of；The alkali source is ammonia, rouge One of fat race amine, aliphatic hydramine and quaternary ammonium base are a variety of；Source of aluminium is Aluminum sol, aluminium salt, aluminium hydroxide and oxidation One of aluminium is a variety of；The titanium source is selected from inorganic titanium salt and/or organic titanate.
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